Caoutchouc substance.



UNITED STATES PATENT onmon,

FRITZ HOFMANN, can. oo'o'mtzcn, mmr MEISENBURG, m) 301mm) nnmanficx, or :snzenmmnn, GERMANY, nssrenons rro FARBENFABRIKEN worm. FBIEDB. BAYER a 00., or Emanuel-m, ems, n oonrona'rron or GERMANY.

CAOUTGIIOUG SUBSTANCE.

'No'Draw'ing.

Specification-of Letters Patent.

application filed October 20, 1am. Serial No. 588,178.

Patented Sept. 30, 1913.

To all whom may con cerna Be it known that we, FRITZ HoF ANN,

Kornmn DnLBRtic-K, doctors of chemists, citizens of the German which the followi is a specification.

We have found at the hydrocarbons of the seriesi i ta he.

in which at least 2 atoms of H are substituted by methyl (the simplest alkyl group of the formula 0,,H groups, for example:

cm on on, cn-cn (DH-42H; CH1: 0/ 8 u CH3 '01:, d-cu, t n na on, 12o rag n 11;0113 3H, 311:, AH, I lH-CHa, Hs,

v C a are converted by polymerization into new caoutchouc substances, which may replace natural caoutchouc in its chemical and techv nical applications The process for producing the new eaoutchouc substances consists in heatlng these hydrocarbons in an appropriate manner so that mainly the new caout- I chouc substances are produced. The process may also carried out in the-presence of agents which promote polymerization, such as acetic acid, creosote, or which act as diluents, such as benzene.

In order to illustrate our invention the following, examples are given, the partsbeing by weight:

Example 1, 500 parts Ofbeta-gamma-dimethylbutadiene of the formula:

IT- on 1 (E li:

clave to 200 C. or until a testsample after distillation with steam in 'ULZCMO leaves a residue behind which is insoluble in alcohol, but soluble in coaltar-benzene. \Vhen this state is reached, the whole mass is distilled with steam in oacwo wherehyrby-products are removed and a residue is obtained which consists of a tough, elastic mass having 1 properties similar to caoutchouc.

Example 2: Beta gamma dimethylbutadiene is boiled for 2 months with a reverse condenser on the water bath which is heated to about from 8090 (3.; the liquid becomes gradually thicker and forms finally an almost gelatinous mass. The heating'is continued until a test sample after distillation,

. leaves aresid'ue behind which is insoluble in alcohol but soluble in coaltar-benzene. When this stage is reached the whole mass is distilled whereupon unchanged betagamma-dimethylbutadiene is removed and the remaining white elastic mass is heated I in came to about 150 C. in order to re- 1 move the last remnants of the hydrocarbon, 3/ and insignificant quantities of lay-products,

which may have formed. The residue forms an elastic whitish mass insoluble in alcohol and soluble in benzene. It forms a nitrosite which is a yellowish powder which be comes brown and is decomposed on being heated to 155-160 C. Its brom addition product is a brownish-yellow powder which becomes black and is decomposed on being heated from 100 to 110 C. Its ozonid is a colorless oil which detonates when heated. Hydrogen peroxid and acetonyl acetone are produced on heating the ozonid with water.

The formation of hydrogen peroxid can be proved by the' known test with titanic acid; that of ,acetonyl acetone by preparing the oximeof the M. P. 1351" and the known product with nitric acid C H,N O melting at 128 C. (see Bem'ckte a'er deutschen chemiscben Gesellschaft 24, page 1305).

Example 3: Alphmalpha-dimethylbutadiene is heated for eight weeks to -100 C. or until a test sample after distillation with steam in vacuo leaves a residue behind which is insoluble in alcohol but soluble in coaltar-benzene and the product of the reaction is then worked up as described in Example 1. i

Example 4: 1000 parts of alpha-alpha-dimethylbutadiene of the formula:

and 5 parts of acetic acid. are heated for 12 hours in an autoclave to 200 C. or until a test sample after distillation with steam in vac-up leaves a residue behind which is insoluble in alcohol but soluble in coal tar benzene. When this stage is reached steam, finally in vacuo is passed through until all by-products are removed and the residue is a caoutchouc like substance.

The new caoutchoucsubstances are whitish substances soluble in benzene and insoluble in alcohol. They are free from protein substances which are always contained in the natural caoutchouc and play an important part in it with regard to the elasticity of the natural caoutchouc. They form ozonids, nitrosites and brom addition products.

,Our method of polymerization'may also be applied to mixtures of these poly-methylsubstituted erythrenes and the mixtures of.

these poly-methyl-substituted erythrenes with other hydrocarbons of the erythrene series and similar groups in various proportions and the thus formed mixtures of new caoutchouc substances may be employed in the arts. I Our new caoutchouc substances described herein maybe vulcanized and such vulcanmix our new caoutchouc substances wit izedcaoutchouc substances may be used in thev Same manner as vulcanized natural natural caoutchouc and subject this mixture to vulcanization.

We claim 4 1. As a new product a caoutchouclike substance comprising poly-methyl-substituted erythrene caoutchouc soluble in coal tar benzene and insoluble in alcohol.

2. As anew product a caoutchouclike substance comprisin di-substituted erythrene caoutchouc sblu le in coal tar benzene and insoluble in alcohol.

3. As a new product a caoutchouclike substance comprising .beta-gammwsubstisubstance ,carbon in the carbon in the presence of an acid.

4. As a new product a caoutchouclike substance comprising. dimethyl-substituted erythrene caoutchouc soluble in coal tar benzene and insoluble in alcohol.

5. As a new product a caoutchouclike comprising beta gamma dimethyl-butadiene caoutchouc, which-is characterlzed by being a whitish substance soluble in coal tar benzene and insoluble in alcohol, forming a .nitrosite which is a yellowish powder which becomesbrown and is decomposed on being heated to 155-160 C.; forming a brom addition product which is a brownish-yellow powder ,which becomes black and is decomposed on being heated to 100110 C. forming an ozonid which is a colorless oil detonating when heated, the

' ozonid furnishin H 0 and acetonylacetone by treatment'wit boiling water; and in the vulcanized form is a whitish not adhesive powder, substantially as described.

6. The process of producing a caoutchouclike substance which comprises polymerizing a poly-methyl-substituted erythrene hydrocarbon until a product results insoluble in alcohol and separating the caoutchouclike substance from the' byproducts formed during the polymerization reaction.

7. The process of producing a caoutchouclikesubstance which comprises heating-a poly-methyl-substituted erythrene hydrocarbon until a product results insoluble in alcohol and separating the caoutchouclike substance from the byproducts formed during the polymerization reaction.

8. The process of producing a caoutchouclike substance which comprises polymerizing a poly-methyl-substituted erythrene hydrocarbon until aproduct results insoluble in alcohol'and subjecting the resulting product to vacuum distillation.

9. The process of producing a caoutchouclike substance which comprises polymerizing a poly-methyl-substituted erythrene hydrocarbon by heat-ing until a caoutchouc-like product results insoluble in alcohol but soluble in coal-tar benzene and subjecting the resultin product to vacuum distillation.

. 10. T e process of producing'a caoutchouclike substance which com rises polymerizing a poly-methyl-substituted erythrene hydropresence of an agent of acid reaction. p

11. The process of producing a caoutchouclike substance which comprises polymerizing a poly-methyl-substituted erythrene hydrocarbon in the presence of an, organic agent of acid reaction.

12. The process of producing-a caoutchouclike substance which comprises polymerizing I a poly-methylesubstituted erythrene hydrocarbon in the presence of an organic acid.

14. The process of producing a caoutchouclike substance which comprises polymerizing a poly-methyl-substituted erythrene hydrocarbon by heating in the presence of an a ent of acid reaction until a caoutchouc- 1i e product results insoluble in alcohol but soluble in coal-tar benzene.

15. The process of producing a caoutchouclike substance which comprises polymerizing A a poly-methyl-substituted erythrene hydrocarbon by heating in the presence of an or- 'ganic agent of acid reaction until a caout- 'ehouc-like product results insoluble in alcohol but soluble in coal-tar benzene.

16. The process of producing a caoutchouc-' like substancewhich comprises polymerizing a poly-methyl-substituted erythrene hydrocarbon by heating in the presence of an acid until a caoutchouc-like product results insoluble in alcohol but soluble in coal-tar benzene.

17. The process of producing a caoutchouclike substance which comprises polymerizing a poly-methyl-substituted erythrene hydrocarbon by heatingin the presence of an organic acid until a caoutchouc-like product results insoluble in alcohol but soluble in coal-tar benzene.

18. The process of producing a caoutchouclike substance which comprises polymerizing a beta-gamma-dimethyl erythrene hydrocarbon until a product results insoluble in alcohol and separating the caoutchouclike substance from the byproducts formed during the polymerization reaction.

19. The process of producing a caoutchouc-' like substance which comprlses heating a beta gamma dimethyl erythrene hydrocarbon until a product results insoluble in alcohol and separating the caoutchouclike substance from the byproducts formedduring the polymerization reaction.

20. The process of producing a caoutchouc-f like substance which comprises polymerizing a beta-gamma-dimethyl erythrene hydrocarbon until a roduct results insoluble in alcohol and -sub e'cting the resulting caoutchouc product to vacuum distillation.

21. The process of producing a caoutchouclike substance which comprises polymerizing a beta-gamma-dimethyl erythrene h drocarbon b ing conditions until a. caoutchouc-like substance results insoluble in alcohol but soluble in coal-tar benzene and subjecting the resulting product to vacuum distillation. I 22. The process of producing a caoutchouc I like substance which comprises heating under caoutchoucorm- I a beta-gamma-dimethyl erythrene hydrocarbon in the presence of an agent of acid reaction.

23. The process of producing a caoutchouclike substance which comprises polymerizing a beta-gamma-dimethyl erythrene hydrocarbon in the presence of an organic agent of acid reaction.

24. The process of producing a caoutchouc'- like substance which comprises polymerizing a beta gammadimethyl erythrene hydrocarbon in the presence of an acid.

a .25. The process of producing a caoutchouclike substance which comprises polymerizing a beta gamma dimethyl erythrene hydrocarbon in the presence of an organic acid.

26. The process of producing a caoutchouclike substance which comprises polymerizing a beta gamma dimethyl erythrene hydro carbon ,by heating in the presence of an agent of acid reaction until, a caoutchouclike. substance results insoluble in alcohol but soluble in coal-tar benzene.

27 The process of producing a caoutchouclike substance which comprises polymerizing a beta gamma dimethyl erythrene hydrocarbon by heating in the presence of an organic agent of acid reaction until a caoutchouc-like substance results insoluble in alcohol but soluble in coal-tar benzene.

28. The process of producing a caoutchouclike substance which comprises polymerizing a beta gamma dimethyl erythrene hydrocarbon by heating in the presence of an acid employed hydrocarbon by heating until a test sample after suitable distillation leaves a residue behind which is soluble in coal tar benzene and insoluble in alcohol.

In testimony whereof we have hereunto set our hands in the presence of two sub- 7 scribing witnesses.

FRITZ HOFMANN. [L. 5.] OARL COUTELLE. [I..s.] 'KURT MEISENBIIRG. [L.s.] KONRAD DELBRUCK. [L.s.]

Witnesses:

, CHAS. J WRIGHT, 'I'WALT'ER'VONNEGU'I'.

It is hereby certified that in Letters Patent No. 1,074,432, granted September 30,-

1913, upon the application of Fritz Hofmann, Carl Coutelle, Kurt Meisenburg, and

Konrad Delbriickl of Elherfeld, Germany, for an improvement in Caoutchoue Sub I stances, an error appears in the printed specification requiring correction as follows Page 3, lines 51-52, for the words caoutchonc product read caoutohouc-like product;

and that the said Letters Patent should be read-with this correction therein that .the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 16th day of December, A. D., 1913.

[SEAL] I J. T. NEWTON,

Acting Commissioner of Patents. 

